Nicotine insecticides. Part VII, Search for synergists (continued)

STATE

ROARD
March 1952 E-836

United States Department of Agriculture

Agricultural Research Administration

Bureau of Entomology and Plant Quarantine

NICOTINE INSECTICIDES. Part VII--SEARCH FOR SYNERGISTS (Continued)

By E. L. Mayer, Carl Robertson, and R. H. Nelson, Division of Stored
Product Insect Investigations/^ Bureau of Entomology and Plant Quar-
antine, and C. F. Woodward, Eastern Regional Research Laboratory,
Bureau of Agricultural and Industrial Chemistry

The search for compounds to replace some of the nicotine in insecti-
cides and thus make its use more economical has been continued. This
paper reports results with IOC chemicals that were tested similarly to
those discussed in Parts II and V of this series (E-709 and E-768). The
materials were furnished by the Eastern Regional Research Laboratory
of the Bureau of Agricultural and Industrial Chemistry and were tested
at the Anaheim, Calif., laboratory of the Bureau of Entomology and Plant
Quarantine.

Material and Methods

A dust containing 2 percent of nicotine sulfate and 5 percent of adjunct
was compared with a 5-percent nicotine sulfate standard for leaf-feeding
larvae or a 3.5-percent standard for the pea aphid. The mortality caused
by some mixtures was compared with that induced by the two components
when used separately. The comparisons were made at approximately the
same deposit. All mixtures were diluted with attapulgite.

Some of the materials were chosen at random, but most of them were
selected because of close chemical resemblance to phthalonitrile and
bis(p_-chlorophenyl) sulfide, the two best materials discussed in E-768.

The test insects included third instars of the armyworm (Pseudaletia
unipuncta (Haw.)) and the diamondback moth (Plutella maculipennis (Curt.)),
fourth instars of the green dock beetle (Gastrophysa cyanea Melsh.), and
the second nymphal stage of the pea aphid (Macrosiphum pisi (Kltb.)).

All the larvae were fed dusted foliage in 9 -cm. petri dishes, whereas
the aphids were dusted directly on the plants on which they were feeding
and then confined in battery jars 16.5 cm. in diameter and covered with

1/ Formerly the Division of Control Investigations.

-2 -

cloth caps. In preliminary fumigation tests the insects were placed in
the lower half of a petri dish, a filter paper 11 cm. in diameter dusted
with the toxicant was placed over the dish, and the top half put in place.
This makes a rather close fitting fumigation chamber and, in addition,
keeps the insects from coming into contact with the insecticide. For all
tests the deposits ranged from 75 to 200 micrograms per square centi-
meter. Approximately 35 larvae and 40 or more aphids were used in
each test. Each material was tested against 3 or 4 species. Mortality
counts of the larvae were made after 3 days and those of the aphids
after 1 day.

Phytotoxicity tests with the materials showing the most promise
were made on plants of bean, beet, broccoli, celery, collard, eggplant,
lettuce, pepper, swiss chard, and tomato.

Discussion of Results

A material was considered to be a possible synergist for nicotine
if the mortality caused by a mixture of the two (table 1, column A) was
approximately the same or above that caused by the nicotine standard
(B). If synergism was indicated in tests against two or more species
of insects, the material was later subjected to developmental testing.
The materials in table 1 were selected on this basis and their evaluations
can be found in the A-B column. This table also presents mortalities
caused by dusts containing 2 percent of nicotine as the sulfate (C) and in
some cases 5 percent of adjunct (D) when used alone. Column A-(C + D)
shows the difference between the kill produced by the mixture and the
additive kills of nicotine and adjunct when tested separately.

On the basis of the averages of mortalities of all tests the materials
in table 1 compared favorably with the 5 -percent standard, except tall
oil nitrile (Arneel TOD), bis(p-bromophenyl) sulfide, and bis(p-chloro-
phenyl) disulfide. Of the materials on which a preliminary determination
could be made for the presence of synergism (A-(C + D)), alpha-naphtho-
nitrile and methyleneaminoacetonitrile were good. A single test with
bis(p-chlorophenyl) disulfide against the pea aphid did not show promise.

Alpha-naphthonitrile is a volatile material and in a fumigation test
a 5-percent dust of it killed 64 percent of the armyworms. Fluorene
when mixed with nicotine sulfate was as effective as the standards against
the armyworm and the pea aphid, but no further tests were made, since
its continued use is dangerous to the investigator.

Phytotoxicity tests showed that against five varieties of plants
methyleneaminoacetonitrile, tall oil nitrile, and bis(p-chlorophenyl)
disulfide v/ere not injurious at 1 -percent concentrations. Phenyl
sulfoxide, m-nitrobenzonitrile, and monochlorodibenzothiophene caused
considerable burning, while 2-chlorodibenzothiophene and Aroclor 1232
caused moderate injury. Tests were not made on the other adjuncts
given in table 1.

-3-

Adjuncts in mixtures with nicotine that showed synergism against one
insect only are shown in table 2.

From the data presented six adjuncts were chosen for quantitative
testing- -isophthalonitrile, methyleneaminoacetonitrile, alpha- naphtho-
nitrile, tall oil nitrile, bis(p-bromophenyl) sulfide, and bis(p-chlorophenyl)
disulfide.

The following adjuncts in mixtures with nicotine showed no synergism
against the armyworm, the diamondback moth, and the pea aphid:

Acenaphthene

Adiponitrile

m-Aminobenzonitrile

gamma-Aminoisobutyric acid

Anthracene

Benzonitrile

Benzothiazole, 2-mercapto-

Benzoylacetonitrile

di-n-Butylcyanamide

n-Capronitrile

Calcium gluconate

Carbazole

Chloracetonitrile

p-Chlorobenzonitrile

beta-Chloropropionitrile

Cyanoacetamide

Dibenzothiophene, 2,8-dichloro-

Diethyl fumarate

l,l-Dimethyl-2-acetylethylene

oxide
Dimethyl fumarate
5, 5 -Dim ethylhydantoin
Dimethyl maleate
Ditolyl sulfide
2-Ethyl-l-hexanol
Ethyl beta-phenyl-alpha-

cyanoacrylate
Furfuryl alcohol
Glycolonitrile

3 -Hydroxy- 3 -methyl - 2 -butanone
Iso-capronitrile
Isophorone

beta-Isopropoxypropionitrile
Itaconic acid
Metaldehyde
1 -Methylnaphthalene

2 -Methylnaphthalene

1 -Methyl-2-propene-l -ol

1 -Methyl-2^propene-l -ol-acetate

Myrcene

beta-Naphthoylacetonitrile

Paraldehyde

Phenol, 2,2-methylenebis (4-chloro-

Phenol, 2,2-methylenebis [4,6-

dichloro-
gamma- Phenoxybutyronitr ile
Phenylacetonitrile
beta -Phenypropionitr ile
Phenyl sulfide, 4-hydroxy-
Phenyl sulfide, 4-hydroxy-4'-

methyl
Phenyl sulfide, 4-methoxy-4'-

methyl
Phenyl sulfone, 5,5'-dichloro-2-2'-

dihydroxy
Phenyl sulfone, 4 methoxy-
Propionitrile

Red oil nitrile (Arneel ROD)
Stearonitrile (Arneel 18D)
Succinonitrile
Tetrahydrofurfuryl acetate
Tetrahydrofurfuryl alcohol
Thianthrene, 2,6-dichloro-
m-Tolunitrile
o-Tolunitrile
p-Tolunitrile
alpha, alpha, beta-Trichloro-

propionitrile
s-Trioxane
n-Valeronitrile
Veratr aldehyde
p-Xenyl sulfide

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UNIVERSITY OF FLORIDA

-8

3 1262 09239 6356

Table 2. --Adjuncts in mixture with nicotine showing synergism against
one insect only

Adjunct

Armyworm

Diamondback
moth

Pea aphid

Acrylonitrile

n-Butyronitrile

delta -Chlorovaleronitrile

Coco nitrile (Arneel CD)

Cyanamid

Cyanoacetanilide

alpha-Cyanoethyl acetate

Cyanuric acid

Decane nitrile (Arneel 10D)

Dicapryl tetrahydrophthalate

Diethyl phthalate

Ethoxypropionitrile

Lactonitrile

Lauryl cyanide

alpha -Naphthaleneacetonitrile

p-Nitrobenzonitrile

p-Nitrophenylacetonitrile

Phthalamide

Pivalonitrile

Tetradecane nitrile (Arneel 14D)

Thianthrene

Tribromophenyl sulfide

Triethyl phosphate

x
x

x

X
X

X
X
X
X
X
X
X

X
X

X
X